CN113036311A - Porous carbon ball packaged vanadium oxide heterogeneous core-shell ball structure material, preparation method thereof, lithium-sulfur battery diaphragm and lithium-sulfur battery - Google Patents
Porous carbon ball packaged vanadium oxide heterogeneous core-shell ball structure material, preparation method thereof, lithium-sulfur battery diaphragm and lithium-sulfur battery Download PDFInfo
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Abstract
The invention belongs to the field of electrochemical materials, and provides a porous carbon sphere packaged vanadium oxide heterogeneous core-shell sphere structure material, a preparation method thereof, a lithium-sulfur battery diaphragm and a lithium-sulfur battery. The preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material comprises the steps of stirring water, ethanol, ammonia water, tetraethyl orthosilicate, resorcinol and formaldehyde for reaction to obtain a carbon-coated silicon dioxide core-shell structure, then carbonizing, adding the carbon-coated silicon dioxide core-shell structure into a sodium hydroxide solution to obtain hollow porous carbon spheres, mixing ammonium metavanadate, ethanol and nitric acid to obtain a vanadium oxide solution, adding the hollow porous carbon spheres, and carrying out hydrothermal reaction after ultrasonic treatment to obtain a product. The amount of vanadium oxide precursors entering the porous carbon spheres is controlled by adjusting ultrasonic time, so that the artificial controllability of the nano structure is realized, the product takes nonpolar carbon spheres as a surface layer, has an adsorption effect on polysulfide, and can show high conversion efficiency when sulfur exists in the inner layer.
Description
Technical Field
The invention belongs to the field of electrochemical materials, and particularly relates to a porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material, a preparation method thereof, a lithium-sulfur battery diaphragm and a lithium-sulfur battery.
Background
The lithium-sulfur battery has high theoretical energy density (2600Wh kg-1) and specific capacity (1675 mAh g-1), and in addition, sulfur has low toxicity and environmental friendliness and is cheap, so the lithium-sulfur battery is considered as the most potential next-generation energy storage system. However, the lithium sulfur battery also has the following problems: firstly, because of uneven lithium deposition, lithium dendrites can be formed in the circulation process, so that the lithium anode can be damaged, inactivated or even turned into dead lithium, the consumption of the electrolyte is greatly increased, and the reversibility of the electrolyte and the lithium anode is reduced. In addition, sharp lithium dendrites can puncture the membrane causing short circuits and thermal runaway. Secondly, the volume expansion is large (79 percent) in the charging and discharging process, so that the structure is easy to damage. Thirdly, the sulfur anode can generate soluble lithium polysulfide (LiPSs) in the charging and discharging processes, and the conductivity of the sulfur anode is low. The LiPSs shuttle between the positive and negative poles, causing loss of positive active substances and inactivation of negative materials, and the process is called shuttle effect, which not only causes continuous capacity attenuation and low coulombic efficiency, but also poisons the lithium negative pole and generates unnecessary intermediate phase. These two major problems result in poor practical electrochemical performance of lithium sulfur batteries.
There are currently two strategies to address the "shuttle effect" present with sulfur anodes: firstly, a sulfur anode is bound into a porous main body material, such as porous carbon, graphite and a conductive polymer, and LiPSs are packaged into the main body material through physical adsorption or chemical bonds; and preparing a multifunctional diaphragm. The diaphragm can not only prevent the contact of the positive electrode and the negative electrode, but also be used as a molecular sieve to prevent the LiPSs from shuttling between the positive electrode and the negative electrode, and the shuttling effect is inhibited.
At present, one of the functional modification modes of the diaphragm is to modify the diaphragm by using a porous material, such as porous carbon, but most of the conductive materials are nonpolar, the adsorption to polysulfide is mainly physical adsorption, and the coulombic efficiency is low. Secondly, the diaphragm is modified by using materials such as carbon, sulfide and the like doped with elements (such as N), so that the diaphragm has stronger chemical adsorption capacity and can effectively capture the LiPSs in the electrolyte, but the quantity of the absorbed and captured LiPSs is increased in proportion to the mass of the modified materials, therefore, the more the quantity of the absorbed and captured LiPSs is, the thicker the thickness of the modified layer of the diaphragm is, the diffusion of ions can be seriously influenced, and the rate capability is greatly reduced.
Disclosure of Invention
The invention aims to solve the problems and provides a porous carbon sphere-encapsulated vanadium oxide heterogeneous core-shell sphere structure material, a preparation method thereof, a lithium-sulfur battery diaphragm and a lithium-sulfur battery.
The invention provides a preparation method of a porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material, which is characterized by comprising the following steps: step 1, adding water, ethanol and ammonia water into a reaction vessel for mixing, adding tetraethyl orthosilicate into the reaction vessel for stirring reaction, adding resorcinol and formaldehyde water solution into the reaction vessel for stirring reaction, and obtaining a carbon-coated silicon dioxide core-shell structure; step 2, placing the carbon-coated silicon dioxide core-shell structure in an inert atmosphere for carbonization, adding the carbonized carbon-coated silicon dioxide core-shell structure into a sodium hydroxide solution, and stirring for reaction to obtain a hollow porous carbon sphere; step 3, adding ammonium metavanadate powder into an ethanol solution, stirring and dispersing to obtain a mixed solution, adding a nitric acid solution into the mixed solution, and stirring to react to obtain a vanadium oxide solution; step 4, adding the hollow porous carbon spheres obtained in the step 2 into the vanadium oxide solution, and then carrying out ultrasonic treatment on the vanadium oxide solution containing the hollow porous carbon spheres to obtain a pre-prepared solution; and 5, sealing the prefabricated solution obtained in the step 4, and carrying out hydrothermal reaction to obtain the porous carbon sphere-packaged vanadium oxide heterogeneous core-shell sphere structure material, wherein in the step 4, the mass-volume ratio of ammonium metavanadate to ethanol solution is 0.2-0.3: 35-45, and the ultrasonic treatment time is 3-4 h.
In the preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material provided by the invention, the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material can also have the following characteristics: in the step 1, the mass ratio of water, ethanol, ammonia water (25 wt%), tetraethyl orthosilicate, resorcinol and formalin (37 wt%) is 138.1: 25.0: 6.8: 8.0: 1.0: 1.5, in the step 5, the temperature of the hydrothermal reaction is 160-200 ℃, and the reaction time is 12-24 h.
In the preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material provided by the invention, the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material can also have the following characteristics: wherein, in the step 2, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
The preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material provided by the invention has the characteristics that the preparation method further comprises the following steps: a purification step, wherein the purification step is operated as follows: and washing and drying the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material to obtain the purified porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material.
The preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material provided by the invention also has the following characteristics: wherein, in the purification step, the drying condition is vacuum, the drying temperature is 60-120 ℃, and the drying time is 6-12 h.
The invention provides a porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material which is characterized by comprising the following components in parts by weight: the shell is composed of carbon elements, the thickness of the shell is about 12nm, the core is located in the shell and is composed of vanadium oxide, and the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material is prepared by a preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material.
The invention provides a lithium-sulfur battery separator having the following features, including: the membrane comprises a membrane body and a modification layer, wherein the modification layer covers the surface of the membrane body, and is composed of porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure materials.
The present invention provides a lithium-sulfur battery having features comprising: the battery comprises a battery shell, a counter electrode, a working electrode, electrolyte and a diaphragm, wherein the diaphragm is a lithium-sulfur battery diaphragm.
Action and Effect of the invention
According to the preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material (hereinafter referred to as porous carbon sphere material), hollow porous carbon spheres are prepared to serve as a shell of the porous carbon sphere material, ammonium metavanadate, ethanol solution and nitric acid solution are mixed to obtain vanadium oxide solution, then the hollow porous carbon spheres are added with the vanadium oxide solution, vanadium oxide can enter the carbon spheres through holes of the hollow porous carbon spheres after ultrasonic treatment, and then the carbon spheres are sealed to carry out hydrothermal reaction, so that vanadium oxide grows in the hollow porous carbon spheres to obtain the porous carbon sphere material. According to the invention, the amount of the vanadium oxide precursor entering the porous carbon spheres can be effectively controlled by adjusting the ultrasonic time, different nanostructures can be obtained in the subsequent hydrothermal process, the amount of the vanadium oxide precursor entering the porous carbon spheres is different, and the shapes and the sizes of the nanostructures grown after hydrothermal reaction are also different, so that the artificial controllability of the nanostructures is realized, meanwhile, the cheap ammonium metavanadate, ethanol, nitric acid and the like are adopted as raw materials, the preparation cost is low, the whole preparation process is simple to operate, easy to realize and easy to realize industrial large-scale production.
The porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material (hereinafter referred to as porous carbon sphere material) comprises a shell and a core packaged in the shell, wherein the shell is composed of carbon elements, the thickness of the shell is about 12nm, and the core is composed of vanadium oxide. The lithium-sulfur battery diaphragm provided by the invention is provided with a diaphragm body and a modification layer coated on the surface of the diaphragm body, wherein the modification layer is made of a porous carbon sphere material. The porous carbon sphere material takes nonpolar carbon spheres as a surface layer, has good physical adsorption effect on polysulfide, and can show extremely high conversion efficiency under the condition that the inner layer contains sulfur. The polar vanadium oxide in the carbon spheres can form a strong chemical bond with polysulfide to anchor the polysulfide, a sulfur-rich high-concentration polarization space is formed in the carbon layer, and an extremely high diffusion barrier is generated, so that the lithium polysulfide is prevented from diffusing to the negative electrode. Meanwhile, the original positive concentration gradient fields of lithium polysulfide on the inner surface and the outer surface of the carbon layer are destroyed by the sulfur concentration in the small inner space of the carbon ball, so that the carbon layer can adsorb polysulfide, the shuttle effect is effectively inhibited, the performance of the lithium-sulfur battery is greatly improved, and the lithium-sulfur battery diaphragm is applied to the lithium-sulfur battery, so that the lithium-sulfur battery diaphragm has good lithium ion transmission performance, excellent mechanical strength, durability and electrochemical performance.
Drawings
FIG. 1 is a Transmission Electron Micrograph (TEM) of solutes in a pre-prepared solution of example 1 according to the present invention at different magnifications;
FIG. 2 is a morphology diagram of a porous carbon sphere-encapsulated vanadium oxide heterogeneous core-shell sphere structure material obtained in example 1 of the present invention;
fig. 3 is a photograph and a Scanning Electron Microscope (SEM) image of the lithium sulfur battery separator obtained in example 1 of the present invention;
fig. 4 is a graph of rate performance of the lithium sulfur battery obtained in example 1 of the present invention;
FIG. 5 is a morphology diagram of a porous carbon sphere vanadium oxide heterogeneous core-shell sphere structure material obtained in comparative example 1 of the present invention;
FIG. 6 is a morphology of a pure vanadium oxide structure obtained in comparative example 2 of the present invention;
FIG. 7 is an XRD pattern of the products obtained in example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 8 is a TEM image at different magnifications of the product obtained in comparative example 3 of the present invention;
FIG. 9 is a TEM image at different magnifications of the product obtained in comparative example 4 of the present invention.
Detailed Description
In order to make the technical means, creation features, achievement purposes and effects of the present invention easy to understand, the following embodiments specifically describe the porous carbon sphere-encapsulated vanadium oxide heterogeneous core-shell sphere structure material, the preparation method thereof, the lithium sulfur battery diaphragm and the lithium sulfur battery with reference to the accompanying drawings.
The starting materials and reagents used in the examples of the present invention were all purchased from general commercial sources, unless otherwise specified.
The preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material (hereinafter referred to as porous carbon sphere material) comprises the following steps:
And 2, after the stirring in the step 1 is finished, collecting the precipitate through centrifugation, washing the precipitate with deionized water and ethanol, and drying in vacuum to obtain the carbon-coated silicon dioxide core-shell structure.
And 3, placing the carbon-coated core-shell structure obtained in the step 2 in an inert atmosphere, carbonizing, adding the carbonized carbon-coated silicon dioxide core-shell structure into a sodium hydroxide solution, and stirring for reaction to obtain the hollow porous carbon spheres.
And 4, adding ammonium metavanadate powder into the ethanol solution, stirring and dispersing to obtain a mixed solution, adding the nitric acid solution into the mixed solution, and stirring to react to obtain a vanadium oxide solution.
And 5, adding the hollow porous carbon spheres obtained in the step 3 into a vanadium oxide solution, and carrying out ultrasonic treatment on the vanadium oxide solution containing the hollow porous carbon spheres to obtain a prefabricated solution.
And 6, sealing the prepared solution obtained in the step 4, and then carrying out hydrothermal reaction to obtain the porous carbon sphere material.
In the step 1, the concentration of ammonia water is 25%, the concentration of formalin is 37%, and the mass ratio of water, ethanol, ammonia water, tetraethyl orthosilicate, resorcinol and formalin is 138.1: 25.0: 6.8: 8.0: 1.0: 1.5. the ethanol is low molecular weight alcohol, and the larger the alcohol concentration is, the larger the diameter of the obtained silicon dioxide spherical particle is; the ammonia actually functions to adjust the PH of the solution, the more basic the silica spheres obtained are of larger diameter. To obtain the porous carbon sphere material with the preset size, the mass ratio of water, ethanol, ammonia water, tetraethyl orthosilicate, resorcinol and formalin needs to be kept unchanged.
In step 3, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
In the step 4, the mass-to-volume ratio of the ammonium metavanadate to the ethanol solution is 0.2-0.3: 35-45.
In step 5, the time of ultrasonic treatment is 3h-4 h.
In the step 6, the temperature of the hydrothermal reaction is 160-200 ℃, and the reaction time is 12-24 h.
The preparation method of the lithium-sulfur battery diaphragm comprises the following steps:
and step S1, uniformly dispersing the porous carbon sphere material in an ethanol solution to obtain a pre-coating solution.
And step S2, uniformly coating the pre-coating solution on the surface of the diaphragm body, and drying in vacuum at the temperature of 30 ℃ to obtain the lithium-sulfur battery diaphragm.
Wherein, the diaphragm body is a polypropylene diaphragm, and the polypropylene diaphragm is a commercial diaphragm Clegard 2400.
The preparation method of the lithium-sulfur battery comprises the following steps:
the lithium-sulfur battery diaphragm is a diaphragm, wherein metal lithium is used as a counter electrode, sulfur is used as a working electrode, 1M LiPF6 dissolved in a mixed solution of Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) (the volume ratio is 1:1) is used as an electrolyte, and the lithium-sulfur battery diaphragm is used as the diaphragm. And assembling the battery in a glove box filled with argon, and standing for 8 hours after the battery is assembled to obtain the lithium-sulfur battery.
< example 1>
In the embodiment, the porous carbon sphere-packaged vanadium oxide heterogeneous core-shell sphere structure material, the lithium-sulfur battery diaphragm, the lithium-sulfur battery and the preparation method are explained in detail.
The preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material (hereinafter referred to as porous carbon sphere material) of the embodiment is as follows:
And 2, after the stirring in the step 1 is finished, collecting the precipitate through centrifugation, washing the precipitate with deionized water and ethanol, and drying in vacuum for 12 hours at the temperature of 60 ℃ to obtain the carbon-coated silicon dioxide core-shell structure.
And 3, placing the carbon-coated core-shell structure obtained in the step 2 in a nitrogen atmosphere, carbonizing at 700 ℃ for 5 hours at a heating rate of 2 ℃/min, etching the carbon-coated silicon dioxide core-shell structure in a water bath at 60 ℃ by using 2M sodium hydroxide solution, and removing silicon dioxide to obtain the hollow porous carbon ball.
And 4, dispersing 0.234g of ammonium metavanadate powder into 40mL of ethanol, adding 2mL of 65% nitric acid solution, and stirring for 30min to obtain a vanadium oxide solution.
And 5, adding 20mg of the hollow porous carbon spheres obtained in the step 3 into the vanadium oxide solution, and carrying out ultrasonic treatment on the vanadium oxide solution for 3 hours to obtain a prefabricated solution.
And 6, sealing the prepared solution, adding the solution into a 50mL hydrothermal kettle, carrying out hydrothermal reaction at 180 ℃ for 20h, and naturally cooling. And after the pre-prepared solution is cooled to room temperature, performing centrifugal filtration to collect precipitates to obtain the porous carbon sphere material.
And 7, washing the porous carbon sphere material by using deionized water and absolute ethyl alcohol, drying for 12 hours in vacuum at the temperature of 60 ℃, and then drying for 10 hours in vacuum at the temperature of 120 ℃ to obtain the purified porous carbon sphere material.
The preparation method of the lithium-sulfur battery diaphragm in the embodiment is as follows:
and step S1, uniformly dispersing the porous carbon sphere material in an ethanol solution to obtain a pre-coating solution.
And step S2, uniformly coating the pre-coating solution on the surface of the diaphragm body, and drying in vacuum at the temperature of 30 ℃ to obtain the lithium-sulfur battery diaphragm.
Wherein, the diaphragm body is a polypropylene diaphragm, and the polypropylene diaphragm is a commercial diaphragm Clegard 2400.
The lithium sulfur battery of this example was prepared as follows:
the lithium-sulfur battery diaphragm is a diaphragm, wherein metal lithium is used as a counter electrode, sulfur is used as a working electrode, 1M LiPF6 dissolved in a mixed solution of Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) (the volume ratio is 1:1) is used as an electrolyte, and the lithium-sulfur battery diaphragm is used as the diaphragm. And assembling the battery in a glove box filled with argon, and standing for 8 hours after the battery is assembled to obtain the lithium-sulfur battery.
The lithium sulfur battery obtained in this example was subjected to electrochemical performance test using an electrochemical analyzer NEWARE.
Fig. 1 is a Transmission Electron Microscope (TEM) image of the solute in the pre-prepared solution in this example at different magnifications, and fig. 2 is a morphology image of the porous carbon sphere-encapsulated vanadium oxide heterogeneous core-shell sphere structure material obtained in this example.
FIG. 2 includes a Scanning Electron Microscope (SEM) image of a porous carbon ball-packaged vanadium oxide heterogeneous core-shell ball structure material, a TEM image of a porous carbon ball-packaged vanadium oxide heterogeneous core-shell ball structure material, an overall Element distribution diagram (Element Mapping) of a porous carbon ball-packaged vanadium oxide heterogeneous core-shell ball structure material, a spatial distribution diagram of carbon elements in a porous carbon ball-packaged vanadium oxide heterogeneous core-shell ball structure material, a spatial distribution diagram of oxygen elements in a porous carbon ball-packaged vanadium oxide heterogeneous core-shell ball structure material, and a spatial distribution diagram of vanadium elements in a porous carbon ball-packaged vanadium oxide heterogeneous core-shell ball structure material.
As shown in fig. 1 and 2, the porous carbon sphere material comprises a shell and an inner core, wherein the shell is a porous carbon sphere composed of carbon elements and has a thickness of about 12nm, and the inner core is positioned inside the shell and is composed of vanadium oxide. After the ultrasonic treatment is carried out for 3 hours, the content of vanadium oxide in the porous carbon spheres is higher, and the content of vanadium oxide in the solution is lower. In the subsequent growth process of vanadium oxide in hydrothermal reaction, the vanadium oxide can not nucleate and grow on the outer surface of the porous carbon sphere due to the low content of vanadium oxide in the solution, and a mutually cross-linked network structure is formed in the ultrasonic process due to the high content of vanadium oxide in the porous carbon sphere, so that sufficient conditions are provided for the subsequent growth of vanadium oxide under the action of hydrothermal reaction. The porous carbon spheres as the shell not only provide nucleation sites for the growth of vanadium oxide in the hydrothermal reaction process, but also limit the growth area of vanadium oxide and encapsulate the vanadium oxide in the porous carbon spheres.
Fig. 3 (a) is a photograph of the lithium-sulfur battery separator obtained in this example; (b) is an SEM image of a lithium sulfur battery separator; (c) is a larger-magnification SEM image of a lithium sulfur battery separator.
As shown in fig. 3 (a), the surface modification layer of the lithium-sulfur battery separator obtained by the coating process is relatively flat and uniform, and the coating process ensures that the surface of the separator can be completely covered by the active material for modification; as can be seen from (b) in fig. 3, the diaphragm obtained by uniformly coating and drying the pre-coating solution has small overall surface fluctuation, carbon sphere particles (i.e., particles with lighter color in SEM image) are uniformly dispersed on the surface, and the surface appearance is relatively flat; as shown in fig. 3 (c), the flocculent fibers are carbon nanotubes used in the modification, and the carbon spheres are coated by the carbon nanotubes and fixed on the surface of the diaphragm, so that the carbon spheres have certain mechanical properties and ensure the stability in the circulation process.
Fig. 4 is a graph comparing rate performance of the lithium sulfur battery obtained in this example and a commercial battery.
As shown in fig. 4, the capacity fade of the lithium-sulfur battery obtained in this example was significantly less than that of the general commercial battery in the case of high-rate charge and discharge, and the lithium-sulfur battery obtained in this example exhibited excellent performance at high current density.
When the current density was restored from 5C to 0.05C, the specific discharge capacity of the lithium-sulfur battery obtained in this example was significantly higher than that using the unmodified Clegard2400 separator, and the capacity fade was also minimal compared to the first discharge.
< example 2>
The porous carbon sphere-encapsulated vanadium oxide heterogeneous core-shell sphere structure material and the preparation method are explained in detail in the embodiment.
The preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material (hereinafter referred to as porous carbon sphere material) of the embodiment is as follows:
And 2, after the stirring in the step 1 is finished, collecting the precipitate through centrifugation, washing the precipitate with deionized water and ethanol, and drying in vacuum for 12 hours at the temperature of 60 ℃ to obtain the carbon-coated silicon dioxide core-shell structure.
And 3, placing the carbon-coated core-shell structure obtained in the step 2 in a nitrogen atmosphere, carbonizing at 700 ℃ for 5 hours at a heating rate of 2 ℃/min, etching the carbon-coated silicon dioxide core-shell structure in a water bath at 60 ℃ by using 2M sodium hydroxide solution, and removing silicon dioxide to obtain the hollow porous carbon ball.
And 4, dispersing 0.25g of ammonium metavanadate powder into 40mL of ethanol, adding 2mL of 65% nitric acid solution, and stirring for 30min to obtain a vanadium oxide solution.
And 5, adding 25mg of the hollow porous carbon spheres obtained in the step 3 into the vanadium oxide solution, and carrying out ultrasonic treatment on the vanadium oxide solution for 3 hours to obtain a prefabricated solution.
And 6, sealing the prepared solution, adding the solution into a 50mL hydrothermal kettle, carrying out hydrothermal reaction at 180 ℃ for 20h, and naturally cooling. And after the pre-prepared solution is cooled to room temperature, performing centrifugal filtration to collect precipitates to obtain the porous carbon sphere material.
And 7, washing the porous carbon sphere material by using deionized water and absolute ethyl alcohol, drying for 12 hours in vacuum at the temperature of 60 ℃, and then drying for 10 hours in vacuum at the temperature of 120 ℃ to obtain the purified porous carbon sphere material.
< example 3>
The porous carbon sphere-encapsulated vanadium oxide heterogeneous core-shell sphere structure material and the preparation method are explained in detail in the embodiment.
The preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material (hereinafter referred to as porous carbon sphere material) of the embodiment is as follows:
And 2, after the stirring in the step 1 is finished, collecting the precipitate through centrifugation, washing the precipitate with deionized water and ethanol, and drying in vacuum for 12 hours at the temperature of 60 ℃ to obtain the carbon-coated silicon dioxide core-shell structure.
And 3, placing the carbon-coated core-shell structure obtained in the step 2 in a nitrogen atmosphere, carbonizing at 700 ℃ for 5 hours at a heating rate of 2 ℃/min, etching the carbon-coated silicon dioxide core-shell structure in a water bath at 60 ℃ by using 2M sodium hydroxide solution, and removing silicon dioxide to obtain the hollow porous carbon ball.
And 4, dispersing 0.3g of ammonium metavanadate powder into 40mL of ethanol, adding 2mL of 65% nitric acid solution, and stirring for 30min to obtain a vanadium oxide solution.
And 5, adding 30mg of the hollow porous carbon spheres obtained in the step 3 into the vanadium oxide solution, and carrying out ultrasonic treatment on the vanadium oxide solution for 3 hours to obtain a prefabricated solution.
And 6, sealing the prepared solution, adding the solution into a 50mL hydrothermal kettle, carrying out hydrothermal reaction at 180 ℃ for 20h, and naturally cooling. And after the pre-prepared solution is cooled to room temperature, performing centrifugal filtration to collect precipitates to obtain the porous carbon sphere material.
And 7, washing the porous carbon sphere material by using deionized water and absolute ethyl alcohol, drying for 12 hours in vacuum at the temperature of 60 ℃, and then drying for 10 hours in vacuum at the temperature of 120 ℃ to obtain the purified porous carbon sphere material.
< example 4>
The porous carbon sphere-encapsulated vanadium oxide heterogeneous core-shell sphere structure material and the preparation method are explained in detail in the embodiment.
The preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material (hereinafter referred to as porous carbon sphere material) of the embodiment is as follows:
And 2, after the stirring in the step 1 is finished, collecting the precipitate through centrifugation, washing the precipitate with deionized water and ethanol, and drying in vacuum for 12 hours at the temperature of 60 ℃ to obtain the carbon-coated silicon dioxide core-shell structure.
And 3, placing the carbon-coated core-shell structure obtained in the step 2 in a nitrogen atmosphere, carbonizing at 700 ℃ for 5 hours at a heating rate of 2 ℃/min, etching the carbon-coated silicon dioxide core-shell structure in a water bath at 60 ℃ by using 2M sodium hydroxide solution, and removing silicon dioxide to obtain the hollow porous carbon ball.
And 4, dispersing 0.3g of ammonium metavanadate powder into 40mL of ethanol, adding 2mL of 65% nitric acid solution, and stirring for 30min to obtain a vanadium oxide solution.
And 5, adding 35mg of the hollow porous carbon spheres obtained in the step 3 into the vanadium oxide solution, and carrying out ultrasonic treatment on the vanadium oxide solution for 4 hours to obtain a prefabricated solution.
And 6, sealing the prepared solution, adding the solution into a 50mL hydrothermal kettle, carrying out hydrothermal reaction at 180 ℃ for 20h, and naturally cooling. And after the pre-prepared solution is cooled to room temperature, performing centrifugal filtration to collect precipitates to obtain the porous carbon sphere material.
And 7, washing the porous carbon sphere material by using deionized water and absolute ethyl alcohol, drying for 12 hours in vacuum at the temperature of 60 ℃, and then drying for 10 hours in vacuum at the temperature of 120 ℃ to obtain the purified porous carbon sphere material.
< comparative example 1>
The preparation method of the porous carbon sphere vanadium oxide heterogeneous core-shell sphere structure material (hereinafter referred to as sphere structure material) of the comparative example is as follows:
And 2, after the stirring in the step 1 is finished, collecting the precipitate through centrifugation, washing the precipitate with deionized water and ethanol, and drying in vacuum for 12 hours at the temperature of 60 ℃ to obtain the carbon-coated silicon dioxide core-shell structure.
And 3, placing the carbon-coated core-shell structure obtained in the step 2 in a nitrogen atmosphere, carbonizing at 700 ℃ for 5 hours at a heating rate of 2 ℃/min, etching the carbon-coated silicon dioxide core-shell structure in a water bath at 60 ℃ by using 2M sodium hydroxide solution, and removing silicon dioxide to obtain the hollow porous carbon ball.
And 4, dispersing 0.234g of ammonium metavanadate powder into 40mL of ethanol, adding 2mL of 65% nitric acid solution, and stirring for 30min to obtain a vanadium oxide solution.
And 5, adding 20mg of the hollow porous carbon spheres obtained in the step 3 into the vanadium oxide solution, and performing ultrasonic treatment on the vanadium oxide solution for 1 hour to obtain a prefabricated solution.
And 6, sealing the prepared solution, adding the solution into a 50mL hydrothermal kettle, carrying out hydrothermal reaction at 180 ℃ for 20h, and naturally cooling. And after the pre-prepared solution is cooled to room temperature, performing centrifugal filtration to collect precipitates to obtain the spherical structure material.
And 7, washing the ball structure material by using deionized water and absolute ethyl alcohol, drying for 12 hours in vacuum at the temperature of 60 ℃, and then drying for 10 hours in vacuum at the temperature of 120 ℃ to obtain the purified ball structure material.
Fig. 5 is a morphology chart of the spherical structural material obtained in this comparative example.
As shown in fig. 5, after 1 hour of ultrasonic treatment, the vanadium oxide precursor entering the porous carbon spheres through the pores of the porous carbon spheres is less, the solution outside the porous carbon spheres still contains more vanadium oxide, and in the subsequent hydrothermal reaction, the vanadium oxide is mainly attached to the surfaces of the porous carbon spheres in a rod-like manner, but also grows inside the porous carbon spheres, so that the vanadium oxide exists on the inner and outer surfaces of the porous carbon spheres, and the vanadium oxide is distributed more uniformly and grows in a substantially uniform manner. The porous carbon spheres not only provide nucleation sites for vanadium oxide in the hydrothermal process, but also provide comfort for the growth area of vanadium oxide.
< comparative example 2>
The preparation method of the pure vanadium oxide structure of this comparative example is as follows:
And 2, carrying out ultrasonic treatment on the vanadium oxide solution for 3 hours to obtain a prefabricated solution.
And 3, sealing the prepared solution, adding the solution into a 50mL hydrothermal kettle, carrying out hydrothermal reaction at 180 ℃ for 20h, and naturally cooling. And after the pre-prepared solution is cooled to room temperature, centrifugally filtering and collecting precipitates to obtain a pure vanadium oxide structure.
And 4, washing the vanadium oxide sphere structure by using deionized water and absolute ethyl alcohol, drying for 12 hours in vacuum at the temperature of 60 ℃, and then drying for 10 hours in vacuum at the temperature of 120 ℃ to obtain the purified pure vanadium oxide structure.
FIG. 6 is a morphology chart of a pure vanadium oxide structure obtained in this comparative example.
As shown in fig. 6, after the hydrothermal reaction, the vanadium oxide grows disorderly, there are more concentrated parts in the shadow inside the pure vanadium oxide structure, and the pure vanadium oxide structure is a homogeneous solid sphere.
X-ray diffraction analysis was performed on the porous carbon sphere material obtained in example 1, the sphere structure material obtained in comparative example 1, and the pure vanadium oxide structure obtained in comparative example 2, to obtain fig. 7.
Fig. 7 is an XRD spectrum of the products obtained in example 1, comparative example 1 and comparative example 2 of the present invention.
As shown in FIG. 7, the peaks of the XRD patterns of the three substances are substantially the same and are similar to V6O13The crystal phases of JCPDS No.71-2235 correspond to each other, which shows that the three substances have vanadium oxide with the same crystal structure, and the vanadium oxide encapsulated in the carbon spheres still retains the original physicochemical properties.
< comparative example 3>
In the comparative example, on the basis of example 1, only the ethanol in the step 4 is replaced by the ethylene glycol, and the other conditions are not changed, so that the ethylene glycol porous carbon sphere material is obtained.
Fig. 8 is a TEM image of the ethylene glycol porous carbon sphere material obtained in the present comparative example at different magnifications.
< comparative example 4>
In the comparative example, on the basis of example 1, only the ethanol in the step 4 is replaced by the mixed solution of isopropanol and glycerol, and the rest conditions are not changed, so that the mixed alcohol porous carbon sphere material is obtained.
Fig. 9 is a TEM image of the mixed alcohol porous carbon sphere material obtained in this comparative example at different magnifications.
As can be seen from a comparison of fig. 2 with fig. 8 and 9, ethanol has a relatively low surface tension at 20 ℃, so that the ethanol has a better wettability in the carbon aerogel material, and thus when ethanol is used as a dispersant, the vanadium oxide has the best effect of growing in the hollow porous carbon spheres.
Effects and effects of the embodiments
According to the preparation method of the porous carbon sphere-encapsulated vanadium oxide heterogeneous core-shell sphere structure material (hereinafter referred to as porous carbon sphere material), hollow porous carbon spheres are prepared to serve as a shell of the porous carbon sphere material, ammonium metavanadate, an ethanol solution and a nitric acid solution are mixed to obtain a vanadium oxide solution, then the hollow porous carbon spheres are added with the vanadium oxide solution, vanadium oxide can enter the carbon spheres through holes of the hollow porous carbon spheres after ultrasonic treatment, and then the carbon spheres are sealed to carry out hydrothermal reaction, so that vanadium oxide grows in the hollow porous carbon spheres to obtain the porous carbon sphere material. According to the invention, the amount of the vanadium oxide precursor entering the porous carbon spheres can be effectively controlled by adjusting the ultrasonic time, different nanostructures can be obtained in the subsequent hydrothermal process, the amount of the vanadium oxide precursor entering the porous carbon spheres is different, and the shapes and the sizes of the nanostructures grown after hydrothermal reaction are also different, so that the artificial controllability of the nanostructures is realized, meanwhile, the cheap ammonium metavanadate, ethanol, nitric acid and the like are adopted as raw materials, the preparation cost is low, the whole preparation process is simple to operate, easy to realize and easy to realize industrial large-scale production.
According to the embodiment, the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material (hereinafter referred to as porous carbon sphere material) comprises a shell and a core packaged in the shell, wherein the shell is composed of carbon elements, the thickness of the shell is about 12nm, and the core is composed of vanadium oxide. The lithium-sulfur battery diaphragm provided by the invention is provided with a diaphragm body and a modification layer coated on the surface of the diaphragm body, wherein the modification layer is made of a porous carbon sphere material. The porous carbon sphere material takes nonpolar carbon spheres as a surface layer, has good physical adsorption effect on polysulfide, and can show extremely high conversion efficiency under the condition that the inner layer contains sulfur. The polar vanadium oxide in the carbon spheres can form a strong chemical bond with polysulfide to anchor the polysulfide, a sulfur-rich high-concentration polarization space is formed in the carbon layer, and an extremely high diffusion barrier is generated, so that the lithium polysulfide is prevented from diffusing to the negative electrode. Meanwhile, the original positive concentration gradient fields of lithium polysulfide on the inner surface and the outer surface of the carbon layer are destroyed by the sulfur concentration in the small inner space of the carbon ball, so that the carbon layer can adsorb polysulfide, the shuttle effect is effectively inhibited, the performance of the lithium-sulfur battery is greatly improved, and the lithium-sulfur battery diaphragm is applied to the lithium-sulfur battery, so that the lithium-sulfur battery diaphragm has good lithium ion transmission performance, excellent mechanical strength, durability and electrochemical performance.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (8)
1. A preparation method of a porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material is characterized by comprising the following steps:
step 1, adding water, ethanol and ammonia water into a reaction vessel for mixing, adding tetraethyl orthosilicate into the reaction vessel for stirring reaction, adding resorcinol and formaldehyde water solution into the reaction vessel for stirring reaction, and obtaining a carbon-coated silicon dioxide core-shell structure;
step 2, placing the carbon-coated silicon dioxide core-shell structure in an inert atmosphere for carbonization, adding the carbonized carbon-coated silicon dioxide core-shell structure into a sodium hydroxide solution, and stirring for reaction to obtain a hollow porous carbon sphere;
step 3, adding ammonium metavanadate powder into an ethanol solution, stirring and dispersing to obtain a mixed solution, adding a nitric acid solution into the mixed solution, and stirring to react to obtain a vanadium oxide solution;
step 4, adding the hollow porous carbon spheres obtained in the step 2 into the vanadium oxide solution, and then carrying out ultrasonic treatment on the vanadium oxide solution containing the hollow porous carbon spheres to obtain a pre-prepared solution;
step 5, sealing the prefabricated solution prepared in the step 4, performing hydrothermal reaction to obtain a porous carbon sphere-packaged vanadium oxide heterogeneous core-shell sphere structure material,
wherein, in the step 4, the mass-to-volume ratio of the ammonium metavanadate to the ethanol solution is 0.2-0.3: 35-45, and the ultrasonic treatment time is 3-4 h.
2. The preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material according to claim 1, characterized in that:
in the step 1, the mass ratio of water, ethanol, ammonia water, tetraethyl orthosilicate, resorcinol and formalin is 138.1: 25.0: 6.8: 8.0: 1.0: 1.5,
in the step 5, the temperature of the hydrothermal reaction is 160-200 ℃, and the reaction time is 12-24 h.
3. The preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material according to claim 1, characterized in that:
wherein, in the step 2, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
4. The preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material according to claim 1, further comprising:
a purification step of purifying the mixture,
wherein the purification step is performed by: and washing and drying the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material to obtain the purified porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material.
5. The preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material according to claim 4, characterized in that:
wherein, in the purification step, the drying condition is vacuum, the drying temperature is 60-120 ℃, and the drying time is 6-12 h.
6. A porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material is characterized by comprising:
a shell and an inner core, wherein the inner core is provided with a plurality of grooves,
wherein the shell is composed of carbon element and has a thickness of about 12nm,
the inner core is positioned in the shell and consists of vanadium oxide,
the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material is prepared by the preparation method of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material according to any one of claims 1 to 5.
7. A lithium sulfur battery separator, comprising:
a diaphragm body and a decorative layer,
wherein the modification layer covers the surface of the diaphragm body,
the modification layer is composed of the porous carbon sphere packaging vanadium oxide heterogeneous core-shell sphere structure material in claim 6.
8. A lithium sulfur battery, comprising:
a battery case, a counter electrode, a working electrode, electrolyte and a diaphragm,
wherein the separator is the lithium sulfur battery separator described in claim 7.
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